CN103122483A - Method for preparing rare-earth halide blocks - Google Patents

Method for preparing rare-earth halide blocks Download PDF

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CN103122483A
CN103122483A CN2012105645865A CN201210564586A CN103122483A CN 103122483 A CN103122483 A CN 103122483A CN 2012105645865 A CN2012105645865 A CN 2012105645865A CN 201210564586 A CN201210564586 A CN 201210564586A CN 103122483 A CN103122483 A CN 103122483A
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monocrystalline
weight
crystal
water
rare earth
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A.伊尔蒂斯
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Luxium Solutions SAS
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Saint Gobain Cristaux and Detecteurs SAS
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Abstract

The invention relates to a method of preparing a polycrystalline block of a halide of formula AeLnfX(3f+e) in which Ln represents one or more rare earths, X represents one or more halogen atoms selected from the group consisting of Cl, Br and I, and A represents one or more alkali metals selected from the group consisting of K, Li, Na, Rb and Cs, e, which may be zero, being less than or equal to 3f, and f being greater than or equal to 1, having a low water and oxyhalide content, in which the method comprises heating a mixture of, on the one hand, at least one compound having at least one Ln-X bond and, on the other hand, a sufficient amount of NH4X in order to obtain the oxyhalide content, resulting in a molten mass comprising the rare-earth halide, the heating being followed by cooling, and the heating, after having reached 300 DEG C,; never going below 200 DEG C before the molten mass has been obtained. The blocks thus produced allow very pure single crystals having remarkable scintillation properties to be grown.

Description

The preparation method of rare-earth halide blocks
The application is that application number is 200380104320.1, the applying date is on November 13rd, 2003, dividing an application with the topic patent application.
Rare earth halide (representing rare earth with Ln hereinafter), especially during their doped with cerium, the LnBr of doped with cerium particularly 3LnCl with doped with cerium 3Have very favorable scintillation efficiency, can be used for nuclear imaging and spectroscopy (γ takes a picture, petroleum prospecting etc. for positron-emission-tomography method, i.e. PET).In order to obtain satisfactorily these performances, should obtain the large-size crystals of these compounds.Generally speaking, these crystal are monocrystalline.In some special situation, they can be also polycrystalline, and in its polycrystalline, the size of these crystal is approximately one centimetre or several centimetres.But rare earth halide is the compound of some strong moisture absorptions, in case they be heated will with water and and air reaction, generate highly stable oxyhalogenide.It is generally acknowledged, oxyhalogenide content approximately 0.1 % by weight is acceptable, and the crystal that reaches these content is enough transparent in appearance.In addition, some crystal (for example CsI:T1) can have extra high oxygen level (for example approximately 0.2%CsOH) for these scintillation efficiencies that people are concerned about.Yet, the applicant finds, oxyhalogenide content in the rare earth halide crystal is reduced to this value when following, can improve significantly the scintillation efficiency of rare earth halide, luminous efficiency particularly, i.e. the ultraviolet-visible light number of photons of the projectile of every MeV energy emission.
Therefore, the applicant attempts to develop the production method that some can obtain the rare earth halide of pure as far as possible (particularly with regard to oxygen), and namely water-content is significantly less than 0.1 % by weight, and oxyhalogenide is lower than 0.2 % by weight, even lower than 0.1 % by weight, especially lower than 0.05 % by weight.In addition, also should find some can make these halogenide keep preservation (for example in several months) and the treating method of this purity.This is because usually with discontinuous manner growing crystal (being generally monocrystalline), and it relates to storage and outbound stage, therefore can make airborne water and oxygen be easy to pollute rare earth halide.
In addition, the equipment of preparation rare earth halide (as crystal, being generally the raw material of single crystal growing) is difficult to make very much, and they itself can not can cause generating water or the oxygen of not wishing oxyhalogenide with a bit.This is because of the always not exclusively sealing of any equipment, and they always contain some planar water, therefore this preparation method has the pollution of part usually, and usually expects the strong oxidation of gaseous environment impurity, especially for example higher than the strong oxidation under the high temperature of 300 ℃.The present invention also proposes a kind of terms of settlement from this viewpoint, because method of the present invention obtains very pure rare earth halide, even use and beginning to contain absorption, the equipment of absorption or condensation phase water, even between the heating period that causes melting in the situation that in atmosphere, reasonable water and oxygen level are also like this.
The applicant's discovery, the fusing point of mentioning in these crystalline melting points prepared in accordance with the present invention and reference is far apart, and the resulting crystal high purity of this available the present invention (especially oxychloride content is low) effect makes an explanation.Therefore, the LaCl of the present invention's preparation 3Tc be 880 ℃, and these values that prior art is delivered are 852-860 ℃.Similarly, the LaBr of the present invention's preparation 3Tc be 820 ℃, and these values that prior art is delivered are 777-789 ℃.
Especially, the present invention can prepare the monocrystalline with short especially scintillation decay time.Its advantage is that its peak the shortest as far as possible crystal fall time that glimmers is desirable, because temporal resolution is improved like this.In order to carry out this measurement, record the main peak light intensity over time.So the present invention might prepare its principal constituent fall time lower than 40 nanoseconds, even lower than 30 nanoseconds, also even lower than the monocrystalline of 20 nanoseconds.In the application's scope, X represents the halogen atom of a kind of Cl of being selected from, Br, I.Consider that rare earth fluorine is nonhygroscopic, also consider the very special chemical of rare earth fluorine, the present invention will not relate to them.
These monocrystalline of the present invention's preparation also have low especially energy resolution, especially lower than 5%, or even lower than 4%, or even lower than 3.5%.
Usually, can adopt following preparation method to prepare rare earth halide:
1.LaX 3(H 2O) 780 ℃ of lower vacuum hydro-extractions: but the LaOX content that this method obtains is very high, also obtains bum crystal;
2. using gaseous state HCl chlorination solid La more than 500 ℃ 2O 3: this method is because need to use a large amount of gaseous state HCl (a kind of toxic gas) and danger close, and this external industrial assurance chlorination reaction is very difficult fully;
3. make LaX in gaseous state HX 3(H 2O) 7Dehydration.This method is also dangerous because using a large amount of HX; With
4. at about 340 ℃ of lower La 2O 3Powder and gaseous state NH 4Cl reaction: be very difficult fully in industrial assurance chlorination reaction;
" brometo de amonio is to anhydrous Brominated rare earth MBr for file 3Flow process "; " the Less-CommonMetals ", 127 (1987) 155-160 the preparation method of rare earth halide/brometo de amonio title complex has been described and under lower than 20 ℃ of/hour conditions thermolysis generate rare earth halide, but never fusing.When carrying out by this way, this halogenide keeps very high specific surface (higher than 0.1m 2/ g), be conducive to like this moisture absorption and be conducive to generate oxychloride.At this true etching problem of these materials that just greatly restricted of processing below 400 ℃, this is preferably to use in the prior art one of them reason of such low temperature.Use NH 4The heating of the prior art of X compounds generally is no more than 300 ℃ or 400 ℃ because under higher temperature NH 4X disappears because of distillation, and rare earth halide can become to the oxygenizement due to the minor amount of water that exists in gaseous environment and oxygen responsive especially.
Can also mention WO 0160944, WO 0160945 and US 6,451 106 as the prior art file.
The invention solves the problems referred to above.The present invention can access a kind of very pure rare earth halide of polycrystalline bulk, and especially, their rare earth oxyhalide oxide content is lower than 0.2 % by weight, especially lower than 0.1 % by weight, even lower than 0.05 % by weight, also even lower than 0.02 % by weight, and water-content is lower than 0.1 % by weight.
Preparation method of the present invention comprises at least a compound and the NH that contains at least one Ln-X key of heating 4The step of the mixture of X, in formula, Ln represents rare earth, X is selected from Cl, Br and I, described compound and NH 4X may be in title complex chemical combination at least in part, described step obtains containing purpose halogenide melting phase, carries out subsequently cooling step, obtains so at least a described halid solid piece that contains.NH 4Play the effect of oxygen scavenqer when X and oxyhalogenide reaction, therefore remove the oxychloride in rare earth halide, its prerequisite is that these oxychlorides may come from the water of heat-processed middle-weight rare earths halogenide absorption and the reaction of rare earth halide.This purification is based on following reaction principle:
LnOX+2NH 4X→LnX 3+H 2O+2NH 3
Method of the present invention especially can be avoided being adsorption form in mixture or crucible or equipment, is the water of absorption or form complexed, and final and rare earth halide chemical combination generates rare earth oxychloride.Therefore, the oxyhalogenide content of the resulting last piece of the inventive method is than beginning not use NH 4Resulting of the same method of X much lower.Especially, use is difficult to remove the equipment of its planar water just can observe this point, namely usually obtain the equipment of high oxyhalogenide content (for example at least 0.2% oxyhalogenide) in halogenide in the end, and there is no even wittingly oxyhalogenide is added to that in the mixture of beginning, (or content is very low, namely 100ppm is following by weight), even in the situation that common water and oxygen level in this preparation method's gaseous environment.
The polycrystalline block that the present invention obtains is very pure.The present invention in independent heating steps, the effect of the removing oxygen that the existence of ammonium halide is given with melt rare earth halide at once and be combined, in order to its specific surface is significantly reduced, make like this it become more insensitive to humidity when processing storing.At first therefore this halogenide be purified in the first step, secondly be melted in second step, make its oxygenizement to water and oxygen become more insensitive, these first and second steps are completed in same heating steps, in case this means that this mixture reaches 300 ℃ of temperature, just do not allow its temperature turn back to again room temperature before the rare earth halide fusing of needs, even do not allow its temperature lower than 200 ℃.This method for preparing piece of the present invention is carried out under inertia or neutral atmosphere (for example nitrogen or argon gas), but this atmosphere even can contain water and the oxygen of relative high-content, namely in this gaseous atmosphere water and oxygen quality sum lower than 200ppm by weight.Generally speaking, in preparation during piece of the present invention, in inert atmosphere, the content of water is 10-180ppm by weight, and oxygen level is 0.5-2ppm by weight.
This owing to comparing the low airborne impurity few (moisture and oxygen) that absorbs of specific surface with powder, therefore can store and process and keep very pure state.Under these conditions, this can be for the preparation of very pure high quality rare earth halide crystal (normally monocrystalline).
The invention still further relates to a kind of method for preparing piece of the present invention in being rich in the crucible of carbon.And according to prior art, such as the article of the people such as P.Egger on " Crystal Growth " 200 (1999) 515-520, " Ba grows in the glassy carbon crucible 2Y 1-xEr xCl 7(0＜x＜1) can make this crucible pollute this crystal ", and these compositions that consist of theme of the present invention are favourable at rich carbon as melting to prepare of the present invention in the glassy carbon crucible.
The rare earth Ln that the present invention relates to is the rare earth on the periodic table of elements the 3rd hurdle (according to new representation), comprising the lanthanon of Sc, Y, La and Ce to Lu.What relate more specifically to is the described halogenide of the halogenide of Y, La, Gd and Lu, especially doped Ce or Pr.
More particularly, can use general formula A with the rare earth halide of the present invention of piece form preparation eLn fX (3f+e)Expression, in formula, Ln represents one or more rare earths, X represents that one or more are selected from the halogen atom of Cl, Br or I, and A represents one or more basic metal, as K, Li, Na, Rb or Cs, e and f represent following value:
-e can be zero, less than or equal to 3f,
-f is more than or equal to 1.
The atomicity of X is lower, and method of the present invention is more effective.Therefore, the efficient that the inventive method is reduced in oxyhalogenide content in this last piece changes with X character, improves along following direction: I＜Br＜Cl.The ionic radius of Ln is larger, and method of the present invention is more effective.So the efficient that the inventive method is reduced in oxyhalogenide content in this last piece changes with Ln character, increase along following direction: Sc＜Lu＜Y＜Gd＜Pr＜Ce＜La.
The rare earth halide that relates more specifically to is following compound specifically:
-ALn 2X 7, in formula, Ln represents one or more rare earths, and X represents that one or more are selected from the halogen atom of Cl, Br or I, and A represents a kind of basic metal, as Rb and Cs,
-LaCl 3, the 0.1-50 % by weight of can adulterating especially CeCl 3,
-LnBr 3, the 0.1-50 % by weight of can adulterating especially CeBr 3,
-LaBr 3, the 0.1-50 % by weight of can adulterating especially CeBr 3,
-GdBr 3, the 0.1-50 % by weight of can adulterating especially CeBr 3,
-La xLn (1-x)X 3, the 0.1-50 % by weight of can adulterating especially CeX 3, x can be 0-1, and Ln is the rare earth different from La, and X is halogen as previously mentioned,
-La xGd (1-x)Br 3, the 0.1-50 % by weight of can adulterating especially CeBr 3, x can be 0-1,
-La xLu (1-x) Br 3, the 0.1-50 % by weight of can adulterating especially CeBr 3, x can be 0-1,
-Ln ' xLn " (1-x)X′ 3 (1-y)X″ 3y, be two kind halogen, particularly Cl and the Brs different from the X class, x can be 0-1, and y can be 0-1 for Ln ' and Ln in formula " being the two kind rare earths different from the Ln class, X ' and X ",
-RbGd 2Br 7, the 0.1-50 % by weight of can adulterating especially CeBr 3,
-RbLn 2Cl 7, the 0.1-50 % by weight of can adulterating especially CeCl 3,
-RbLn 2Br 7, the 0.1-50 % by weight of can adulterating especially CeBr 3,
-CsLn 2Cl 7, the 0.1-50 % by weight of can adulterating especially CeCl 3,
-CsLn 2Br 7, the 0.1-50 % by weight of can adulterating especially CeBr 3,
-K 2LaCl 5, the 0.1-50 % by weight of can adulterating especially CeCl 3,
-K 2LaI 5, the 0.1-50 % by weight of can adulterating especially CeI 3
Term " doping agent " or " doping " mean a small amount of rare earth that replaces one or more a large amount of rare earths, and these a small amount of and a large amount of rare earths all use symbol Ln to represent.
So it is La or Ce that the present invention can obtain Ln especially, X is the piece of Cl or Br.
The present invention be more particularly directed to the preparation method of a kind of, it is characterized in that the method comprises at least a compound and the NH that contains at least one Ln-X key of heating 4The step of the mixture of X, described compound and NH 4X can be in a kind of title complex chemical combination at least in part, described step obtains containing formula A eLn fX (3f+e)Halid fusing piece after obtaining this fusing piece, carries out cooling step after described heating steps, described heating steps is not reduced to below 200 ℃ before described fusing piece obtaining after reaching 300 ℃.
The compound that contains at least one Ln-X key can be formula A rLn sO uX R+3s-2u, in formula, A, X and Ln have the meaning that provides previously, and r, s and u represent integer or non integer value, and they satisfy following condition together:
R can be 0-2s,
S is more than or equal to 1,
U can be 0-s,
This compound can with water or NH 4X complexing or can be not and its complexing.
In the compound that contains at least one Ln-X key, the oxidation state of Ln is 3, if A is arranged, the oxidation state of A is 1.Especially, r can be zero.U can be zero especially.
Preferably, in the compound that contains at least one Ln-X key, the oxygen amount of being combined with Ln is such, namely adopts oxyhalogenide amount that dissolution method obtains by weight lower than 100ppm.
The compound that contains at least one Ln-X key can be rare earth halide or hydrated rare-earth halogenide.For example, it can be formula LnX 3Or LnX 3(H 2O) n, wherein n is 1-10, or multiple mixture with above chemical formula compound.
The compound that contains at least one Ln-X key can also be the rare earth oxyhalide oxide compound, and it can be the mixture of formula LnXO or multiple given chemical formula compound.Preferably, avoid that preferably LnXO is arranged in starting mixt.So preferably, this starting mixt contains the following LnXO of 100ppm by weight.Generally speaking, this is the Powdered rare earth halide that contains low levels oxyhalogenide and water.This mixture can also contain rare earth oxyhalide oxide compound and NH 4The title complex of X.
This mixture can also contain the water of free form or complex pattern, for example with the water of rare earth halide complexing.Astoundingly, its water yield can be very large, and this point does not cause containing in last polycrystalline block of the present invention the more oxyhalogenide of high-content, as long as this mixture contains the NH of q.s 4X。
This mixture for example can contain equally until the water of 20 % by weight is even higher.It for example can also contain the water lower than 16 % by weight, even lower than the water of 5 % by weight.
At least a compound and the NH that contains at least one Ln-X key 4The mixture of X, two kinds of compounds (if necessary) are at least part of for this when being complex pattern, contain enough NH 4X, making this last piece middle-weight rare earths oxyhalogenide is below 0.2 % by weight, and even the rare earth oxyhalide oxide compound is below 0.1 % by weight, and also even the rare earth oxyhalide oxide compound is below 0.05 % by weight, and more even the rare earth oxyhalide oxide compound is below 0.02 % by weight.
Preferably, in this compound the Ln atom only with X atom or Sauerstoffatom or A atomic linkage.Formula LnX 3(NH 4X) xEspecially this situation of title complex, in formula the Ln atom only with the X atomic linkage.Here, it is believed that without any belonging to NH 4The atom of X and Ln atomic linkage.
Preferably, add a certain amount of NH in this mixture 4X, its amount is following two amount sums at least:
-A) equal one times, preferably three times not with the NH of the Ln mole number of oxygen bonding 4The mole number of X,
-B) equal three times, five times of NH with the Sauerstoffatom mole number of Ln bonding preferably 4The mole number of X.
Especially, this mixture adds a certain amount of NH in the past 4X, its amount is following two amount sums at least:
-A) equal three times not with the NH of the Ln mole number of oxygen bonding 4The X mole number,
-B) equal five times of NH with the Sauerstoffatom mole number of Ln bonding 4The X mole number.
Should be expressly understood, if calculate NH in the computer capacity of A 4During X, just should not consider same NH in the computer capacity of B 4X, vice versa.If this mixture does not contain the oxygen with the Ln bonding, B) NH 4The X amount is zero.
Can think in the application's scope, identical with the mole number of the Sauerstoffatom mole number of Ln bonding and formula LnOX oxyhalogenide, as resulting in the dissolution method that employing the following describes.When oxyhalogenide has formula LnOX, can be easy to by adopting the resulting oxyhalogenide piece of dissolution method to calculate Sauerstoffatom mole number with the Ln bonding.During if any A (being generally Rb or Cs), consider that the possibility that this atom is combined with oxygen is very little, its existence does not affect NH 4The calculating of X amount.
Should be expressly understood, in order to calculate this amount, preferably consider NH all in this mixture 4No matter the X molecule is this NH 4X be complexing or there is no complexing, for example with the rare earth halide complexing or there is no complexing.
This mixture can contain a kind of compound and NH that contains at least one Ln-X key 4The title complex of X.For example, can adopt wet chemical method to prepare this title complex based on following principle:
At first with rare-earth salts, as rare earth oxide or hydrated rare-earth halogenide, be dissolved in corresponding hydracid (if be HCl when namely wishing to obtain muriate, if be HBr when wishing to obtain bromide).In this stage, if target is the halogenide that contains A, add AX (A is generally Rb or Cs).Add ammonium halide toward this solution, preferably every mole of rare earth halide is 1-4 mole of ammonium halide, to obtain a kind of solution.Obtain at last if wish adulterate other rare earth Ln'(such as cerium) Ln rare earth halide (in fact, doping Ln' halogenide) time, when being dissolved in hydracid, for example add the Ln'(of required ratio: if wish to obtain at last the 10%CeX that adulterates 3Anhydrous LnX 3The time, use by LaX 3(H 2O) 7The 10%CeX that obtains 3(H 2O) 7Solution).
This solution is again at baking oven or adopt any suitable method to carry out drying.The formula LnX that obtains 3(NH 4X) x, wherein the salt of x=3.5 is stable, can be stored in sealed vessel.
At least a at least one Ln-X key compound and NH of containing 4Then the mixture of X heat-treats.For this thermal treatment, this mixture to be packed in crucible, it can be made with platinum, charcoal (as graphite), molybdenum, tantalum, boron nitride or silicon-dioxide.This crucible can also be made with the graphite of coating RESEARCH OF PYROCARBON, the graphite of coating carbon SiClx or the graphite of coating boron nitride.Preferably, for this fusing, use the crucible that can make this demoulding when cooling.In order to prepare of the present invention, preferably use the crucible made from a kind of material that contains at least 20 % by weight carbon.A kind of like this material can be for example to use charcoal or graphite, amorphous carbon (or glassy carbon), the graphite (being also glassy carbon) of coating RESEARCH OF PYROCARBON, the graphite of coating carbon SiClx or the graphite (may be pyrolysis) of coating boron nitride to make.Therefore this crucible can apply one deck RESEARCH OF PYROCARBON.This material can comprise graphite base and coating, and this coating can be made with RESEARCH OF PYROCARBON, silicon carbide or boron nitride (may be pyrolysis).This coating is mainly used in blocking the graphite hole.
Then this crucible is placed in sealed furnace, and its atmosphere makes it become inertia through purification, for example first purifies under rough vacuum, then purges with the dry nitrogen air-flow.Then, furnace temperature little by little is raised to until 400 ℃ at least.Remove the water of title complex, then make NH 4The X distillation is deposited on the cold wall in stove downstream.Importantly make this mixture can not be subject to the effect of ambient air, be placed in fully under inert atmosphere, especially higher than 300 ℃, preferably higher than under the inert atmosphere of 200 ℃.Therefore, in this equipment, these possible air intlets should be higher than NH 4The place of X deposition, air can not enter mixture to be purified as a result.
Consider NH in this mixture 4General all excessive this facts of X, the actual temperature of this mixture generally is raised to corresponding to removing NH 4The temperature levels of X, also like this even this sequencing temperature-stable raises.At NH 4In the situation of Cl, this temperature levels is 300-400 ℃.NH not only 4X is when beginning to be free form, and it is all wished like this when being complex pattern.Because the NH that this heat block contains after this temperature levels 4The X much less, impurity (water of existence and oxygen) the institute oxidation of expecting that this mixture also is easy to be existed in gaseous environment, this temperature rises to get higher also just more so (in this stage, the temperature of heat block is generally higher than 300 ℃).It not is this situation that the applicant finds, also may control the oxidation of rare earth halide.
At NH 4After X left this temperature levels, then this temperature should raise fast until be enough to make the temperature (LaCl for example of required rare earth halide fusing 3It is 880 ℃).At NH 4After X leaves this temperature levels, be usually 300-400 ℃, the mixture that has changed with respect to raw material (has lost NH because of it 4X) can be with higher than 50 ℃/hour, especially higher than 100 ℃/hour, even higher than 150 ℃/hour, also even heat higher than the speed of 200 ℃/hour.Generally speaking, consider generally and should protect equipment and materials according to its heat shock resistance intensity, its rate of heating is lower than 600 ℃/hour.During the heating material fusing, preferably make its temperature reach at least one hour higher than temperature of fusion, usually 1-6 hour.
About heating this mixture, in case the temperature of mixture higher than 300 ℃, before required rare earth halide reaches fusing point, does not just allow its temperature turn back to room temperature again, even its temperature also must not be lower than 200 ℃.Preferably in single heating steps with this mixture heating up until fusing before obtaining containing the halid fusing piece of fusing, does not reduce its temperature, even do not reduce momently its temperature yet.Whole heating steps (from room temperature until its fusing) generally carries out less than 10 hours, even less than 6 hours, also even less than 4 hours.
This fusing piece can carry out cooling fast.So be recovered to anhydrous rare-earth halide blocks, it contains the following water of 0.1 % by weight, and the following rare earth oxyhalide oxide compound of 0.2 % by weight, especially the following rare earth oxyhalide oxide compound of 0.1 % by weight, the following rare earth oxyhalide oxide compound of 0.05 % by weight even, the also following rare earth oxyhalide oxide compound of 0.02 % by weight even.This is easy to process and store.Generally speaking, can prepare the per unit piece of 1g at least, the per unit piece of 10g at least especially, the per unit piece of 50g at least even, also the per unit piece of 500g at least even.The apparent density of these pieces is generally at least 75% of theoretical density, even at least 80%, more even at least 85%, suppose that this theoretical density is the density corresponding to the same material in imporosity.Of the present invention is polycrystalline, contains many crystal grain, and its each crystal grain is little monocrystalline.One generally contains at least 100 crystal grain, even at least 1000 crystal grain.Account for more than 10% of whole quality without any crystal grain in this.
Being condensate in ammonium halide on the cold part in stove downstream for example can be used further in method of the present invention at least in part.
In order to measure the ratio of oxyhalogenide in rare earth halide, only need water that they are separated with regard to enough (for example at room temperature), because these oxyhalogenides are water insoluble, these halogenide are water-soluble.Can adopt filter method, for example use polypropylene (PP) strainer to reclaim these oxyhalogenides, then carry out drying at 120 ℃.The situation that contains A (being generally Rb or Cs) for this halogenide, this method can make the AX dissolving, because A does not generate oxyhalogenide.The method of this what is called " dissolution method " or " not dissolving method " is easy to measure formula LnXO oxyhalogenide content, and is also like this when even in this halogenide, A being arranged.
Piece of the present invention can be as the raw material according to these known technology growing crystals (being generally monocrystalline), as so-called Bridgman, Kyropoulos or Czochralski growing technology or employing gradient Mobile Method growing technology.These monocrystalline are very pure, can be used as scintillator material.This crystal preparation method carries out under inert atmosphere (for example nitrogen or argon gas), but this atmosphere even can have relatively high water and oxygen level, and namely the quality sum of water and oxygen is by weight lower than 200ppm in gaseous atmosphere.Generally speaking, at the preparation crystal when (being generally monocrystalline), in inert atmosphere, water-content is 10-180ppm by weight, and in inert atmosphere, oxygen level is 0.5-2ppm by weight.
Due to use as raw material this or these piece surface-area are low, also owing to raising in temperature until during fusing this surface-area do not increase, so this final monocrystalline is very pure, its scintillation efficiency highly significant.Therefore, the invention still further relates to a kind of formula A eLn fX (3f+e)Monocrystalline, its symbol has the meaning that the front has provided, and described monocrystalline contains below 0.2%, especially below 0.1%, even below 0.05%, the following rare earth oxyhalide oxide compound of 0.02 % by weight even also.Especially, when Ln is selected from La, Gd, Y, Lu and Ce, and X is exactly like this when being selected from Cl and Br.More particularly can utilize following monocrystalline:
-always form Ln 1-xCe xBr 3Monocrystalline, in formula, Ln is selected from the mixture of lanthanon or La, Gd, Y, Lu family lanthanon, is selected from especially lanthanon or La, Gd family lanthanon, in formula, x replaces the molar ratio of Ln with cerium, and x is greater than or equal to 0.01 % by mole, strictly lower than 100 % by mole
-always form Ln 1-xCe xCl 3Monocrystalline, in formula, Ln is selected from the mixture of lanthanon or Y, La, Gd, Lu family lanthanon, be selected from especially La, Gd, Lu family's element or its mixture, in formula, x replaces the molar ratio of Ln with cerium, and x is greater than or equal to 1 % by mole, strictly lower than 100 % by mole.
Above-mentioned growth method can obtain large-sized monocrystalline, i.e. 1cm at least 3, 10cm even at least 3, 200cm even at least also 3Monocrystalline.This monocrystalline can cut into suitable size according to desirable application.
Monocrystalline of the present invention has extra high optical efficiency because of its high purity.This optical efficiency is measured with respect to the optical efficiency of the NaI crystal of 600ppm thallium iodide by weight of adulterating specifically, and its energy resolution at 622KeV is 6.8%, and be 1 μ s integral time, and radioactive source is the Cs137 at 622KeV.Use until 320nm is transparent silicone fat that these crystal (NaI or rare earth halide) and photomultiplier cell are tied.Certainly, NaI is polishing towards the output face of photomultiplier cell.Under these measuring conditions, the optical efficiency that the present invention can reach be doping TI NaI crystal optical efficiency at least 90%, under any circumstance all higher than the optical efficiency of using non-crystal of the present invention to reach.
Can use especially the plumbago crucible of platinum crucible or plumbago crucible or coating RESEARCH OF PYROCARBON to prepare this crystal or monocrystalline.
In these embodiment, measured in the following manner energy resolution below: this monocrystalline is cut into 10 * 10 * 5mm sheet.Except one of them large 10 * 10mm, all faces of this sheet all stay as the cutting blank, and are polished with the face that photomultiplier cell (PMT) connects.This crystal is wound around with PTFE (the T é flon) band of multi-thickness, but except the face that connects with PMT.Carry out the preparation of this crystal in lower than the glove box of-40 ℃ at dew point.
Embodiment 1: anhydrous LaCl 3
With 433g La 2O 3Being dissolved in 1380ml 37%HCl is diluted in solution in 2450ml water.Add 497g NH 4Cl.Then be heated to 100 ℃ and boil off water and excessive HCl, obtain LaCl 3(NH 4Cl) 3.5Title complex adopts Karl Fischer method to measure it and contains 0.7 % by weight water.LaCl 3(NH 4Cl) 3.5Title complex is a kind of compound that contains at least one Ln-X key, because it contains the La-Cl key.From meaning of the present invention, itself is also a kind of mixture, and it contains a kind of compound and NH of the Ln-X of having key 4X (is NH in this case 4Cl).In addition, in this mixture, NH 4The amount of X is to make NH 4The X mole number be not 3.5 with the ratio of the Ln mole number of oxygen bonding, this is well corresponding to preferred ratio of the present invention.In addition, due to oxygen and Ln bonding, there is no to calculate the NH that adds 4X is not because this starting mixt contains this generic key.
From room temperature with the heating of 200 ℃/hour of speed until 950 ℃ the time, then in the crucible made from the graphite of pyrolytic carbon coating, the 200g title complex is decomposed, NH 4Cl distils and melts, and described crucible itself is placed in the airtight silica tube with nitrogen purging.This nitrogen atmosphere contains by weight approximately 50ppm water and 1-2ppm oxygen.In this last piece that the employing dissolution method is measured, oxychloride content is 0.01 % by weight.Water-content is lower than 0.1 % by weight (detectability of using method).The quality of gained piece is 651g.
Embodiment 2 (contrast): anhydrous LaC1 3
Strictly undertaken by embodiment 1, just use anhydrous LaC1 3Powder replaces this title complex, and the oxychloride content of this powder is lower than 0.02%, and particle size is submillimeter, adopts the KarlFischer method water-content not detected.
The oxychloride content that adopts dissolution method to measure this last piece is 0.23 % by weight.Water-content is lower than 0.1 % by weight.
Embodiment 3: anhydrous LaBr 3 : Ce
With 300g La 2O 3Being dissolved in 630ml47%HBr is diluted in solution in 2330ml water.Add 682g NH 4Br.Filter gained solution with PP.Then this solution carry out drying with rotatory evaporator in 10 liters of round-bottomed bottles.Adopt Karl Fischer method to measure gained title complex, its formula LaBr 3(NH 4Br) 3.5, contain 0.23 % by weight water.Then get this title complex of 142.6g, use 0.5 % by weight (NH 4Br) 3.5CeBr 3Adulterate, then in plumbago crucible under nitrogen purging with 200 ℃ of/hour heating.Kept 4 hours 30 minutes 860 ℃ of levels.This nitrogen atmosphere contains by weight approximately 50ppm water and 1-2ppm oxygen.The remnants caking of the fusing 76.61g that weighs just contains 0.035% oxybromide LaOBr (adopt not dissolution method measure).Water-content is also lower than 0.1 % by weight.
The statics of fluids density of measuring this by being immersed in hexane is about 4.92g/cm 3, namely 87% of theoretical density, thus good densification proved.
Then this fusing piece is carrying out the crystal growth under nitrogen purging in plumbago crucible in the Bridgman stove.This nitrogen atmosphere contains by weight approximately 50ppm water and 1-2ppm oxygen.The crystal that obtains is transparent, there is no oxybromide inclusion and the bubble of white.The oxybromide content of this crystal is 0.05 % by weight.This crystal block be suitable as scintillator more than 80%.
Embodiment 4: the anhydrous LaBr that uses wet complex preparation 3
Use the title complex LaBr as front embodiment preparation 3(NH 4Br) 3.5, make simultaneously it wetting, in order to contain 14.7 % by weight water, this is to adopt Karl Fischer method to measure.Then get this mixture of 124g (title complex+water), then heat until 860 ℃ with 200 ℃/hour under nitrogen purging in plumbago crucible.Kept 4 hours 30 minutes 860 ℃ of levels.This nitrogen atmosphere contains by weight approximately 50ppm water and 1-2ppm oxygen.The remnants of this fusing caking 64.1g that weighs, it only contains 0.034 % by weight oxybromide (adopt not dissolution method measure).Water-content is lower than 0.1 % by weight.
Embodiment 6: anhydrous GdBr 3
With 271.2g Gd 2O 3Be dissolved in 796g48% HBr and be diluted in solution in 430g water.Then add 661.2g NH 4Br and 855g water.The solution that obtains filters with PP.Then this solution carry out drying with rotatory evaporator in 10 liters of round-bottomed bottles.At this moment obtain 1164g title complex (NH 4Br) 4.5GdBr 3The title complex that obtains contains 6.3% water, and this is to adopt Karl Fischer method to measure.Then take this title complex of 254.7g, it under nitrogen purging in plumbago crucible with 200 ℃ of/hour heating.Kept 1 hour 30 minutes 815 ℃ of levels.This nitrogen atmosphere contains by weight approximately 50ppm water and 1-2ppm oxygen.Sintering and the unfused remaining caking 104.9g that weighs.Therefore be a kind of powdery solid, then be placed under these envrionment conditionss.Reinstall the remaining caking of the aforementioned sintering of 92.7g in stove, under nitrogen purging in plumbago crucible with 200 ℃ of/hour heating.Kept 1 hour 30 minutes 840 ℃ of levels.This nitrogen atmosphere contains by weight approximately 50ppm water and 1-2ppm oxygen.The remnants of this fusing caking 92.7g that weighs contains 0.65 % by weight GdOBr (adopt not dissolution method measure), and to turn back to room temperature before fusing be improperly thereby prove this.
Embodiment 7: anhydrous GdBr 3
This test is used as the title complex (NH according to front embodiment preparation 4Br) 4.5GdBr 3The title complex that obtains contains 6.3 % by weight water, and this is to adopt Karl Fischer to measure.Then get this title complex of 245.7g, it heats until 840 ℃ with 200 ℃/hour in plumbago crucible under nitrogen purging.Kept 1 hour 30 minutes 840 ℃ of levels.This nitrogen atmosphere contains by weight approximately 50ppm water and 1-2ppm oxygen.The remnants of this fusing caking 105.3g that weighs only contains 0.038 % by weight oxybromide GdOBr (adopt not dissolution method measure).This result is more representative, because gadolinium is heavy (so-called yttrium) rare earth, its bromide is very responsive to hydration.
Embodiment 8 (contrast): use LaCl 3 The monocrystalline of powder preparation
Use with embodiment 2 with crowd anhydrous LaCl 3Powder is grown under nitrogen purging in plumbago crucible in the Bridgman stove.This nitrogen atmosphere contains by weight approximately 50ppm water and 1-2ppm oxygen.The bubble that the crystal that obtains has many white oxychloride inclusiones and consists of with filament form along the drawing axle.The oxychloride content of this crystal is 0.25 % by weight.Approximately 90% this crystal block is not suitable for as scintillator.
Embodiment 9: anhydrous RbGd 2 Cl 7
With 138.2g Rb 2CO 3Being dissolved in 242g37%HCl is diluted in solution in 165g water.Filter resulting solution with PP.Then with 433.8g Gd 2O 3Being dissolved in 750g37%HCl is diluted in solution in 482g water.After the dissolving, add rubidium toward filtering solution fully.Add at last 576.2g NH 4Cl and 881g water.Filter the solution that obtains with PP.Its pH is-0.32, and this liquid density is 1.24.Then this solution use rotatory evaporator to carry out drying in 10 liters of round-bottomed bottles.At this moment obtain 1227g (NH 4Cl) 9RbGd 2Cl 7Then take out this title complex of 142.6g, it heats until 660 ℃ with 200 ℃/hour in plumbago crucible under nitrogen purging.Kept 4 hours 30 minutes 660 ℃ of levels like this.This nitrogen atmosphere contains by weight approximately 50ppm water and 1-2ppm oxygen.The remnants of this fusing caking only contains the following GdOCl of 0.05 % by weight (adopt not dissolution method measure).
Embodiment 10: use synthesizing of LaOBr
The following mixture of preparation in the glassy carbon crucible: 0.5874g LaOBr, 1.3585gNH 4Br (namely 5.5 moles) and 10.0678g (NH 4Br) 3.5LaBr 3Title complex.Heat this mixture until 830 ℃ with 200 ℃/hour, kept 2 hours at this temperature levels.This nitrogen atmosphere contains by weight approximately 50ppm water and 1-2ppm oxygen.The insolubles content of this last piece is 0.19 % by weight.
Embodiment 11:LaCl 3 Monocrystalline
Use 1kg LaCl prepared in accordance with the present invention 3Piece wherein contains 10 % by weight CeCl 3, its LaOCl content is lower than 0.05 % by weight.Then this be used for carrying out the growth of Bridgman class in plumbago crucible.This nitrogen atmosphere contains by weight approximately 50ppm water and 1-2ppm oxygen.The crystal that obtains is very transparent.Adopt the oxychloride content of not dissolution method measurement lower than 0.05%.Then from this crystal-cut a slice, its size is 10 * 10 * 5mm, and the scintillation efficiency of its scintillation efficiency and NaI:TI sheet (NaI of 600ppm thallium iodide by weight adulterates) compares, and its alternative is as follows:
Photomultiplier cell: Hamamatsu R-1306
Reference: the NaI crystal of diameter 50mm and length 50mm
Integral time: 1 μ s
The Cs137 of radioactive source: 622KeV.
LaC1 3The crystal light emission is NaI reference crystal photoemissive 93%.Its energy resolution is 3.6%.The principal constituent scintillation decay time was 27 nanoseconds.
Embodiment 12 (contrast): LaCl 3 Monocrystalline
Use the commercially available LaC1 of 1kg 3And CeCl 3Powder (LaOX of embodiment 2 and water-content).CeCl 3Quality account for 10% in these two kinds of powdered mixture quality.Allow these powder melt in plumbago crucible, and carry out the growth of Kyropoulos (KC 01) crystalloid.This nitrogen atmosphere contains by weight approximately 50ppm water and 1-2ppm oxygen.Obtain crystal and be microemulsion.Its insolubles content is 0.1 % by weight.Then this crystal is cut into 10 * 10 * 5mm sheet, according to the same scheme of above-described embodiment, its scintillation efficiency and the scintillation efficiency of NaI:TI sheet are compared.LaCl 3The light emission of crystal is 83% of NaI reference crystal.Its energy resolution is 3.9%.
Embodiment 13 (contrast): LaCl 3 Monocrystalline
Illustrate according to IEEE nuclear science society publication (Publication IEEE transactionson Nuclear science), adopt Bridgman class growth method to prepare crystal in silicon oxide crucibles: " LaCl 3The scintillation properties of crystal: fast, the scintillator of efficient and high energy resolution ".CeCl before the crystal growth 3Quality be 10% of mixture quality.Then this crystal is cut into 10 * 10 * 5mm sheet, according to the same scheme of above-mentioned two embodiment, its scintillation efficiency and the scintillation efficiency of NaI:TI sheet are compared.LaCl 3The light emission of crystal is 87% of NaI reference crystal.Its energy resolution is 4.2%.
Embodiment 14:LaBr 3 Monocrystalline
Use the LaBr of three each 1kg prepared in accordance with the present invention 3, their 0.5 % by weight CeBr that adulterates 3, LaOBr content＜0.05 % by weight like this.This growth that then is used for the Czochralski class in plumbago crucible.This nitrogen atmosphere contains by weight approximately 50ppm water and 1-2ppm oxygen.The crystal that obtains is very transparent.Adopt not dissolution method can not measure the oxychloride content of this.Then this crystal is cut into 10 * 10 * 5mm sheet, according to following proposal, its scintillation efficiency and the scintillation efficiency of NaI:TI sheet is compared:
-photomultiplier cell: Hamamatsu R-1306.
-reference: NaI:TI crystal (Nal adulterated 600ppm thallium iodide by weight), its diameter 50mm, length 50mm.
The energy resolution of-this reference crystal is 6.8% at the Cs137 line.
-these are measured crystal and are wound around with Teflon, and use silicone oil (EDM fluid 200) to connect with becoming photomultiplier cell (PMT).
-integral time: 1 μ s.
The Cs137 of-radioactive source: 622KeV
LaBr 3The light emission of crystal is 147% of NaI reference crystal.Its energy resolution is 4.2%.The principal constituent scintillation decay time was 39 nanoseconds.
Embodiment 15 (contrast): LaBr 3 Monocrystalline
Publication " Applied Physics communication (Applied phys icsLetters) " (the 79th volume according to September 3 calendar year 2001, the 10th phase) explanation, the crystal that adopts Bridgman class growth method to obtain in silicon oxide crucibles compares with the test of front.This crystal also contains 0.5 % by weight CeBr 3Then this crystal is cut into 10 * 10 * 5mm sheet, according to the scheme same with front embodiment, its scintillation efficiency and the scintillation efficiency of NaI:TI sheet is compared.This crystal is microemulsion.LaBr 3The light emission of crystal is 102% of NaI reference crystal.The principal constituent scintillation decay time was 38 nanoseconds.
Embodiment 16:LaCl 3 Monocrystalline
Use the LaCl of three each 1kg prepared in accordance with the present invention 3, their 5 % by weight CeCl that adulterate 3, LaOCl content＜0.05 % by weight like this.This growth that then is used for the Bridgman class in plumbago crucible.This nitrogen atmosphere contains by weight approximately 50ppm water and 1-2ppm oxygen.The crystal that obtains is very transparent.Adopt not dissolution method can not measure the oxychloride content of this.Its content is lower than 0.05 % by weight.Then this crystal is cut into 10 * 10 * 5mm sheet, according to following proposal, its scintillation efficiency and the scintillation efficiency of NaI:TI sheet is compared:
-photomultiplier cell: Hamamatsu R-1306.
-reference: NaI:TI crystal (Nal adulterated 600ppm thallium iodide by weight), its diameter 50mm, length 50mm.
The energy resolution of-this reference crystal is 6.8% at the Cs137 line.
-these are measured crystal and are wound around with Teflon, and use silicone oil (EDM fluid 200) and photomultiplier cell (PMT) to connect.
-integral time: 1 μ s.
The Cs137 of-radioactive source: 622KeV
LaCl 3The light emission of crystal is 98% of NaI reference crystal.Its energy resolution is 4.6%.The principal constituent scintillation decay time was 28 nanoseconds.
Embodiment 17: anhydrous LaCl 3
Carry out as embodiment 1, this is just used platinum crucible to be prepared.This last piece is sticking mutually with this crucible, and its demoulding is than much more difficult with the plumbago crucible of RESEARCH OF PYROCARBON coating.

Claims (29)

1. formula A eLn fX (3f+e)Monocrystalline, it is characterized in that its volume is 10cm at least 3, in formula, Ln represents one or more rare earths, X represents that one or more are selected from the halogen atom of Cl, Br or I, and A represents one or more basic metal, e and f represent following value:
-e is less than or equal to 3f,
-f is more than or equal to 1,
It contains the following rare earth oxyhalide oxide compound of 0.1 % by weight.
2. monocrystalline according to claim 1, wherein e is zero.
3. monocrystalline according to claim 1, is characterized in that described basic metal is K, Li, Na, Rb or Cs.
4. according to claim 1 or 3 described monocrystalline, is characterized in that the content of its oxyhalogenide is lower than 0.05 % by weight.
5. monocrystalline according to claim 4, is characterized in that the content of its oxyhalogenide is lower than 0.02 % by weight.
6. the described monocrystalline of any one according to claim 1,3 and 5, it is characterized in that Ln is selected from La, Gd, Y, Lu and Ce, and X is selected from Cl and Br.
7. monocrystalline according to claim 4, it is characterized in that Ln is selected from La, Gd, Y, Lu and Ce, and X is selected from Cl and Br.
8. according to claim 1, the described monocrystalline of any one in 3,5 and 7, it is characterized in that its volume is 200cm at least 3
9. monocrystalline according to claim 4 is characterized in that its volume is 200cm at least 3
10. monocrystalline according to claim 6 is characterized in that its volume is 200cm at least 3
11. according to claim 1,3,5,7 and 9-10 in the described monocrystalline of any one, it is characterized in that its optical efficiency be adulterate 600ppm thallium iodide by weight the NaI crystal at least 90%, its energy resolution is 6.8% at 622KeV, and be 1 μ s integral time, and radioactive source is at 622KeV 137Cs.
12. monocrystalline according to claim 4, it is characterized in that its optical efficiency be adulterate 600ppm thallium iodide by weight the NaI crystal at least 90%, its energy resolution is 6.8% at 622KeV, be 1 μ s integral time, radioactive source is at 622KeV 137Cs.
13. monocrystalline according to claim 6, it is characterized in that its optical efficiency be adulterate 600ppm thallium iodide by weight the NaI crystal at least 90%, its energy resolution is 6.8% at 622KeV, be 1 μ s integral time, radioactive source is at 622KeV 137Cs.
14. monocrystalline according to claim 8, it is characterized in that its optical efficiency be adulterate 600ppm thallium iodide by weight the NaI crystal at least 90%, its energy resolution is 6.8% at 622KeV, be 1 μ s integral time, radioactive source is at 622KeV 137Cs.
15. according to claim 1,3,5,7, the described monocrystalline of any one in 9-10 and 12-14, it is characterized in that its energy resolution is lower than 5%.
16. monocrystalline according to claim 4 is characterized in that its energy resolution is lower than 5%.
17. monocrystalline according to claim 6 is characterized in that its energy resolution is lower than 5%.
18. monocrystalline according to claim 8 is characterized in that its energy resolution is lower than 5%.
19. monocrystalline according to claim 11 is characterized in that its energy resolution is lower than 5%.
20. monocrystalline according to claim 15 is characterized in that its energy resolution is lower than 4%.
21. monocrystalline according to claim 20 is characterized in that its energy resolution is lower than 3.5%.
22. according to claim 1,3,5,7, the described monocrystalline of any one in 9-10,12-14 and 16-21, it is characterized in that principal constituent fall time is lower than 40 nanoseconds.
23. monocrystalline according to claim 4 is characterized in that principal constituent fall time is lower than 40 nanoseconds.
24. monocrystalline according to claim 6 is characterized in that principal constituent fall time is lower than 40 nanoseconds.
25. monocrystalline according to claim 8 is characterized in that principal constituent fall time is lower than 40 nanoseconds.
26. monocrystalline according to claim 11 is characterized in that principal constituent fall time is lower than 40 nanoseconds.
27. monocrystalline according to claim 15 is characterized in that principal constituent fall time is lower than 40 nanoseconds.
28. monocrystalline according to claim 22 is characterized in that principal constituent fall time is lower than 30 nanoseconds.
29. monocrystalline according to claim 28 is characterized in that principal constituent fall time is lower than 20 nanoseconds.
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